Oxyalkylated aliphatic polyepoxidetreated amine-modified phenol aldehyde resins, and method of making same



United States Patent OXYALKYLATED ALIPHATIC POLYEPOXIDE- TREATED AMlNE-MODIFIED PHENOL ALDE- HYDE RESINS, AND METHOD OF MAKING SAME Melvin De Groote, St. Louis, and Kwan-Ting Shen, Brentwood, Mo., assignors to Petrolite Corporation, Wilmington, Del., a corporation of Delaware No Drawing. Original application July 30, 1953, Serial No. 371,413, now Patent No. 2,771,454, dated November 20, 1956. Divided and this application September 12, 1956, Serial No. 609,357

7 Claims. (Cl. 26045) The present invention is a continuation-in-part of our copending application, Serial No. 364,504, filed June 26, 1953, now U. S. Patent 2,771,428, and a division of our copending application Serial No. 371,413, filed July 30, 1953,-.now U. S. Patent 2,771,454.

Our invention is concerned with new chemical products or compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type and particularly petroleum emulsions. Our invention is also concerned with the application of such chemical products or compounds in various other arts and industries as well as with methods of manufacturing the new chemical products or compounds which are of outstanding value in demulsification.

The present invention is concerned with a three-step manufacturing method involving (1) condensing certain phenol aldehyde resins, hereafter described in detail, with certain basic hydroxylated polyamine's, hereinafter described in detail, and formaldehyde; (2) oxyalkylation of the condensation product with certain nonaryl hydrophile polyepoxides hereinafter described in detail; and (3) oxyalkylation of the previously oxyalkylated resin condensate with certain monoepoxides, also hereinafter described in detail.

The present invention is characterized by analogous compounds derived from diglycidyl ethers Which do not introduce any hydrophobe properties in its usual meaning but, in fact, are more apt to introduce hydrophile properties. Thus, the diepoxides employed in the present invention are characterized by the fact that the divalent radical connecting the terminal epoxide radicals contains less than 5 carbon atoms in an uninterrupted chain.

The diepoxides employed in the present process are obtained from glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, glycerol, diglycerol, triglycerol, and similar compounds. Such products are well known and are characterized by the fact that there are not more than 4 uninterrupted carbon atoms in any group which is part of the radical joining the epoxide groups. Of necessity such diepoxides must be nonaryl or aliphatic in character. The diglycidyl ethers of co-pending application, Serial No. 364,503, are invariably and inevitably aryl in character. The diepoxides employed in the present process are usually obtained by reacting a glycol or equivalent com- 7 pound, such as glycerol or diglycerol, with epichlorohydrin and subsequently with an alkali. Such diepoxides have been described in the literature and particularly the patent literature. 'See, for example, Italian Patent No. 400,973, dated August 8, 1951; see, also, British Patent 518,057, dated December 10, 1938; and U. S. Patent No. 2,070,990, dated February 16, 1937, to Gross et al. Reference is made also to U. S. Patent 2,581,464, dated January 8; 1952, to Zech. This particular last mentioned "ice 2 patent describes a composition of the following general formula:

Halogen z in which x is at least 1, z varies from less than 1 to more than 1, and x and z together are at least 2 and not more 6, and R is the residue of the polyhydric alcohol remaining after replacement of at least 2 of the hydroxyl groups thereof with the epoxide ether groups of the above formula, and any remaining groups of the residue being free hydroxyl groups. I I

It is obvious from what' is said in the patent that variants can be obtained in which the halogen is replaced by a hydroxyl radical; thus, the formula would become 0 LHHHQGE] Reference to being thermoplastic characterizes them as being liquids at ordinary temperature or readily convertible to liquids by merely heating below the point of pyrolysis and thus differentiates them from infusible resins. Reference to being soluble in an organic solvent means any of the usual organic solvents such as alcohols, ketones, esters, ethers, mixed solvents, etc. Reference to solubility is merely to differentiate from a reactant which is not soluble and might be not only insoluble but also infusible. Furthermore, solubility is a factor insofar that it sometimes is desirable to dilute the compound containing the epoxy rings before reacting with an amine condensate. In such instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation as, for example, kerosene, benzene, toluene, dioxane, possibly various ketones, chlorinated solvents, dibutyl ether, dihexyl ether, ethyleneglycol diethylether, diethyleneglycol diethylether, and dimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to the 1,2-epoxy ring. The 1,2-epoxy ring is sometimes referred to as the oxirane ring to distinguish it from other epoxy rings. cated otherwise, will be used to mean the oxirane ring, i. e., the 1,2-epoxy ring. Furthermore, where a compound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course,

1,2-epoxide rings or oxirane rings in the alpha-omega position. This is a departure of course, from the standpoint of strictly formal nomenclature as in the example of the simplest diepoxide which contains at least 4 carbon atoms and is formally described as 1,2-epoxy-3,4epoxybutane (1,2-3,4 diepoxybutane).

It well may be that even though the previously suggested formula represents the principal component, or components, of the resultant or reaction product described Hereinafter the word epoxy unless indi-' in the previous text, it may-be important to note that somewhat similar compounds, generally of much higher molecule weight, have been described as complex resinous epoxides which are polyether derivatives of polyhydric compoundscontaining an average of more than, one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. The compounds here included are limited to the monomers or the low molal members of; such series and generally contain two epoxiderings per moleculeand may be entirely free from a hydroxyl group. This is important because the instant invention is directed towards products which are not insoluble resins, and havecertain solubility characteristics not inherent in, the usual thermosetting resins. Simply for purpose of illustrating to show a typical diglycidyl ether of the kind herein employed, reference is made to the following formula:

or if derived from cyclic diglycerol the structure would be thus:

or the equivalent compound wherein the ring structure involves only 6 atoms, thus:

Commercially available compounds seem to be largely the former with comparatively small amounts, in fact, comparatively minor amounts, of the latter.

Having obtained a reactant having generally 2 epoxy rings as depicted: in the next to last formula preceding, or low. molal: polymers thereof, it becomes obvious the reaction can take place with any amine-modified phenolaldehyde resin by virtue of the fact that there are always present reactive hydroxyl. groups which are part of the phenolic nuclei and there-may be present reactive hydrogen atoms attached to anitrogen atom, or an oxygen atom, depending on the-presence ofa hydroxylated group or secondary aminogroup.

To illustratethe products which represent the subject matter of the present invention reference will be-rnade toa reaction involving: a mole of the oxyalkylation agent, i. e., the compoundlhaving two oxirane rings and an amine condensate. Proceeding with the example previously. described it is obvious the reaction ratio of two moles of the amine condensate to one mole of the oxyalkylating agent gives a product which may be indicated as.- follows:

Condensate) (Condensate) in which n is a small wholenumher, less than 1. an usually less than 4, and including 0, and R represents a. divalent radical as previously described being free from any radical having more than 4 uninterrupted carbon atoms in a singlechain, and the characterization condensate is simply an abbreviation for the condensate which is described in greater detail subsequently.

Such intermediate product in turn also must be soluble but solubility is not limited to an organic solvent but may include water, or for that matter, a solution of water containing an acid such as hydrochloric acid, acetic acid, hydroxyacetic acid, gluconic acid, etc. In other words, the nitrogengroups present, whether two or more, may or may not be significantly basic and it is immaterial whether aqueous solubility represents an anhydro base orthe free base (combination with water) or a salt form such as the acetate, chloride, etc. The purpose in the instance is to differentiate from insoluble resinous materials, particularly those resulting from gelation or crosslinking. Not only does this properly serve to differentiate from instances Where an insoluble material is desired but also serves to emphasize the fact that in many instances the preferred compounds have distinct watersolubility or are distinctly dispersible in 5% gluconic acid. For instance, the products freed from any solvent can be shaken with 5 to 20 times their weight of 5% gluconic acid at ordinary temperature and show at least some tendency towards being self-dispersing. The solvent which is generally tried is xylene. If xylene alone does not serve then a mixture of xylene and methanol, for instance, parts of xylene and 20 parts of methanol, or 70 parts of xylene and.30 parts of methanol, can be used. Sometimes it is desirable to add a small amount of: acetone tothe xylene-methanol mixture, for instance, 5% to 10% of acetone.

A. mere examination of the nature of the products before and. after treatment with a polyepoxide reveals that the polyepoxide by and large introduces increased hydrophile character or, inversely, causes a decrease in hydrophobe character. However, the solubility characteristics ofithe final product, i. e., the product obtained by oxyalkylation with a monoepoxide, may vary all over the. map. This is perfectly understandable because ethylene oxide, glycide, and to a lesser extent methyl glycide, introduce predominantly hydrophile character, while propylene oxide and more especially butylene oxide, introduce primarily hydrophobe character. A mixture of the various oXides will produce a balancing in solubility characteristics or in the hydrophobe-hydrophile character so as to be about the same as prior to oxyalkylation with the monoepoxide.

The oxyalkylated polyepoxide treated condensates obtainedin the manner described are, in turn, oxyalkylation-susceptible and valuable derivatives can be obtained by further reaction with other alkylene oxides, for instance, styrene oxide (phenylethylene oxide), cyclohexylethylene oxide, ethylene imine, propylene imine, acrylonitrile, etc.

Similarly, the oxyalkylated polyepoxide-derived compounds can be reacted with a product having both a nitrogen group anda 1,2-epoxy group, such as 3-dialkylaminoepoxypropane. See U. S. Patent No. 2,520,093, dated'August 22, 1950; to Gross.

Although the herein describedproducts have a number ofindustrial applications, they are of particular value for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprise fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

The new products are useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid washingof building stone and brick; as wetting agents and Spreaders in the application of asphalt in road building and the like; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles, such as sewage, coal washing Waste water, and various trade wastes and the like; as germicides, insecticides; emulsifying agents, as, for example, for cosmetics, spray oils, water-repellent textile finishes; and lubricants, etc.

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the water-in-oil type, we particularly prefer to use those which as such or in the formof the free base or hydrate, i. e., combination with water or particularly in the form of a low molal organic acid salt such as the gluconates or the acetate or hydroxyacetate, have sufiiciently hydrophile character to at least meet the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a water-insoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various condensation products as such or in the form of the free base or in the form of the acetate, may not necessarily be xylene soluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a water-soluble solvent such as ethylene-glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification testincludes such obvious variant.

For purpose of convenience what is said hereinafter will be divided into eight parts:

Part 1 is concerned with the hydrophile nonaryl polyepoxides and particularly diepoxides employed as reactants;

Part 2 is concerned with the phenol-aldehyde resin which is subjected to modification by condensation to yield the amine-modified resin;

Part 3 is concerned with appropriate basic hydroxylated polyamines Which may be employed in the preparation of the herein-described amine-modified resins;

Part 4 is concerned with reactions involving the resin, the amine, and formaldehyde to produce specific products or compounds which are then subjected to reaction with polyepoxides, and particularly diepoxides;

Part 5 is concerned with reactions involving the two preceding types of materials and examples obtained by such reaction. Generally speaking, this involves nothing more than reaction between 2 moles of a previouslyprepared amine-modified phenol-aldehyde resin condensate as described and one mole of a hydrophile polyepoxide so as to yield a new and larger resin molecule, or comparable product;

Part 6 is concerned with the use of monoepoxide in oxyalkylating the products described in Part 5, preceding, i. e., those derived by means of reaction between a polyepoxide and an amine-modified phenol-aldehyde resin as described;

Part 7 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products; and

Part 8 is concerned with uses for the products herein described, either as such or after modification, including any applications other than those involving resolution of petroleum emulsions of the water-in-oil type.

PART 1 Reference is made to previous patents as illustrated in the manufacture of the nonaryl polyepoxides and particularly diepoxides employed as reactants in the instant invention. The simplest diepoxide is probably the one derived from 1,3-butadiene or isoprene. Such derivatives are obtained by the use of peroxides or by other suitable means and the diglycidyl ethers may be indicated'thusr H H H H In some instances the compounds are essentially derivatives of etherized epichlorohydrin or methyl epichloro-v hydrin. Needless to say, such compounds can be derived from glycerol monochlorohydrin by etherization prior to ring closure. An example is illustrated in the previously mentioned Italian Patent No. 400,973:

Another type of diepoxide is diisobutenyl dioxide'as described in aforementioned U. S. Patent No. 2,070,9f)0, dated February 16, 1937, to Groll, and is of the following formula CH3 CH3 The diepoxides previously described may be indicated in which R represents a hydrogen atom or methyl radical and R" represents the divalent radical uniting the two terminal epoxide groups and n is the numeral 0 to 1. As previously pointed out, in the case of the butadiene derivative, n is 0. In the case of diisobutenyl dioxide R" is CH CH and n is 1. In another example pre viously referred to R" is CH OCH and n is 1.

However, for practical purposes the only diepoxide available in quantities other than laboratory quantities is a-derivative of glycerol or epichlorohydrin. This particular diepoxide is obtained from diglycerol which is largely acyclic diglycerol, and epichlorohydrin or equivalent thereof in that the epichlorohydrin itself may supply the glycerol or diglycerol radical in addition to the epoxy rings. As has been suggested previously, instead of starting with glycerol or a glycerol derivative one could start with any one of a number of glycols or polyglycols and it is more convenient to include as part of the terminal oxirane ring radical the oxygen atom that was derived from epichlorohydrin or, as might be the case, methyl epichlorohydrin. So presented the formula becomes:

H H H H H H HCC-C-O[R1]OO-OC}I H H In the following formula R is selected from groups such as the following:

It is to be noted that in the above epoxides there is a complete absence of (a) aryl radicals and (b) radicals in which or more carbon atoms are united in a'single uninterrupted single group. R is inherently hydrophile in character as indicated by the fact that it is specified that the precursory diol or polyol OHROH must be water-soluble in substantially all proportions, i. e., water miscible.

Stated another way, what is said previously means that a polyepoxide such as is derived actually or theoretically, or 'at least derivable,

from the diol HOROH, in which the oxygen-linked hydrogen atoms were replaced by in which R is C H (OH) it is obvious that reaction with another mole of epichlorohydrin with appropriate ring closure would produce a triepoxide or, similarly, if R happened to be C H (OH)OC H (OH), one could obtain a tetraepoxide. Actually, such procedure generally yields triepoxides, or mixtures with higher epoxides and perhaps in other instances mixtures in which diepoxides are also present. Our preference is to use the diepoxides.

There is available commercially at least one diglycidyl ether free from aryl groups and also free from any radical having 5 or more carbon atoms in an uninterrupted chain. This particular diglycidyl ether is obtained by the use of epichlorohydrin in such a manner that approximately 4 moles of epichlorohydrin yield one mole of the diglycidyl ether or, stated another way, it can be considered as being formed from one mole of diglycerol and 2 moles of epichlorohydrin so as to give the appropriate diepoxide. The molecular weight is approximately 370 and the number of epoxide groups per molecule are approximately 2. For this reason in the first of a series of subsequent examples this particular diglycidyl ether is used, although obviously any of the others previously described would be just as suitable. For convenience, this diepoxide will be referred to as diglycidyl ether A. Such material corresponds in a general way to the previous formula.

Using laboratory procedure we have reacted diethyleneglycol with epichlorohydrin and subsequently with alkali so as to produce a product which, on examination, corresponded approximately to the following compound:

The molecular weight of the product was assumed to be 230 and the product was available in laboratory quantities only. For this reason, the subsequent table referring to the use of this particular diepoxide, which will be referred to as diglycidyl ether B, is in grams instead of pounds.

Probably :the simplest terminology for these polyepoxides, and particularly diepoxides, to differentiate from comparable aryl compounds is to use the terminology epoxyalkanes and, more particularly, polyepoxyalkanes 8 or diepoxyalkanes. The difficulty is that the majority of these compounds represent types in which a carbon atom chain is interrupted by an oxygen atom and, thus, they are not strictly alkane derivatives. Furthermore, they may be hydroxylated or represent a heterocyclic ring. The principal class properly may be referred to as polyepoxy-polyglycerols, or diepoxypolyglycerols.

Other examples if diepoxides involving a heterocyclic ring having, for example, 3 carbon atoms and 2 oxygen atoms, are obtainable by the conventional reaction of combining erythritol with a carbonyl compound, such as formaldehyde or acetoneso as to form the 5-membered ring, followed by conversion of the terminal hydroxyl groups into epoxy radicals.

See also Canadian Patent No. 672,935.

PART 2 It is well known that one can readily purchase on the open market, or prepare, fusible, organic solventsoluble, water-insoluble resin polymers of a composition approximated in an idealized form by the formula In the above formula 11 represents a small whole number varying from 1 to 6, 7, or 8, or more, up to probably 10 or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., It varies from 1 to 4; R represents an aliphatic hydrocarbon substituent, generally an alkyl radical having from 4 to 15 carbon atoms, such as butyl, amyl, hexyl, decyl or dodecyl radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic solvent-soluble does not mean it is necessarily soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previously noted. However, when obtained from a difunctional phenol, for instance para-phenylphenol, one may obtain a resin which is not soluble in a non-oxygenated solvent, such as benzene, or xylene, but requires an oxygenated solvent such as low molal alcohol, dioxane, or diethyleneglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and non-oxygenated) will serve. See Example 9a of U. S. Patent No. 2,499,365, dated March 7, 1950, to De Groote and Keiscr.

The resin herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote and Keiser.

If one selected a resin of the kind just described previously and reacted approximately one mole of the resin with two moles of formaldehyde and two moles of a basic hydroxylated polyamine as specified, following the same idealized over-simplification previously referred to, the resultant product might be illustrated thus:

The basic hydroxylated amine may be designated thus:

RI HN' In conducting reactions of this kind one does not necessarily obtain a hundred percent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde, or only one mole of the amine may combine with the resin molecule, or even to a very slight extent, if at all, 2 resin units may combine without any amine in the reaction product, as indicated in the following formulas:

As has been pointed out previously, as far as the resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

R R n R in which R is the divalent radical obtained from the particular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears .to be described best in terms of the method of manufacture.

Resins can be made using an acid catalyst or basic catalyst or a catalyst having neither acid nor basic properties in the ordinary sense or without any catalyst at all. It is preferable that the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong acid should be neutralized. Similarly, if a strong base is used as a catalyst it is preferable that the base be neutralized although We have found that sometimes the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount may be as small as a 200th of a percent and as much as a few lOths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer, i. e., one having just 3 units, or just 4 units, or just 5 units, or just 6 units, etc. It is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be such that it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

In the actual manufacture of the resins we found no reason for using other than those which are lowest in price and most readily available commercially. For pur-- poses of convenience suitable resins are characterized in the following table:

E R Mfol. wt.

xo res n ample R a g derived or molecule number from (based on n+2) Tertiary bntyl Para Formal- 3. 5 882. 5

Secondary butyl. 3. 5 882. 5 Tertiary amyl 3. 5 959. 5 Mixed secondary 3. 5 805. 5

and tertiary amyl. Propyl Para do 3. 5 805. 5 Tertiary hexyl. d 3. 5 1, 036. 5 Oct 1 3. 5 1, 190. 5 3. 5 1, 267. 5 3. 5 1, 344. 5 3. 5 1, 498. 5 3. 5 945. 5

3. 5 1, 148. 5 Nonyl do 3.5 l, 456. 5 Tertiary butyl Propional- 3. 5 1, 008.5

dehyde. Tertiary amyl 3. 5 1, 085. 5 N n 1 3. 5 1, 393. 5 4. 2 996. 6

21a Tertiary amyl 4. 2 1, 083. 4 22a 'Nony 4. 2 1, 430. 6 23a Tertiary butyl 4. 8 1, 094. 4 24a Tertiary amyl 4. 8 1, 189. 6 Nonyl 4.8 1, 570. 4 Tertiary amyL. 1. 5 604. 0 Hexyl 1. 5 653. 0 d 1. 5 688.0

35a Amyl do do.. 2.0 692. 0 36a Hexyl do do 2.0 748. 0

PART 3 As has been pointed out, the amine herein employed as a reactant is a hydroxylated basic polyamine and preferably a strongly basic polyamine having at least one secondary amino radical, free from primary amino. groups, free from substituted imidazoline groups, and free from substituted tetrahydropyrimidine groups, in which the hydrocarbon radicals present, whether monovalent or divalent are alkyl, alicyclic, arylalkyl, or heterocyclic in character, subject of course to the inclusion of a hydroxyl group attached to a carbon atom which in turn is part of a monov'alent or divalent radical.

Previous reference has been made to a number of polyamines which are satisfactory for use as reactants in the instant condensation procedure. They can be ob tained by hydroxylation of low cost polyamines. The cheapest amines available are polyethylene amines and polypropylene amines. In the case of the polyethylene amines there may be as-many as 5, 6 or 7 nitrogen atoms;

Such amines are susceptible to terminal alkylation or the equivalent, i. e., reactions which convert the terminal primary amino group or groups into a secondary or tertiary amine radical. In the case of polyamines having at least 3 nitrogen atoms or more, both terminal groups could be converted into tertiary groups, or one terminal group could be converted into a tertiary group and the other into a secondary amino group. In the same way, the polyamines can be subjected to hydr-oxyalkylation by reaction with ethylene oxide, propylene oxide, glycide, etc. In some instances, depending on the structure, both types of reaction may be employed, i. e., one, type to introduce a hydroxyl ethyl group, for example, and another type to introduce a methyl or ethyl or ethyl radical.

By way of example the following formulas are included. It will be noted they include such polyamines which, instead of being obtained from ethylene dichloride. pro-- pylene dichloride, or the like, are obtained from dichloro-;

11 ethyl ethers in which the divalent radical has a carbon atom chain interrupted by an oxygen atom:

C 2H5 C 3H5 N C 211411; C 2H4N HO C2114 C2H4OH CH3 CH HOCZHt HOCzH4 Another procedure for producing suitable polyamines is a reaction involving first an alkylene imine, such as ethylene imine or propylene imine, followed by an alkylene oxide, such as ethylene oxide, propylene oxide or glycide.

What has been said previously may be illustrated by reactions involving a secondary alkyl amine, or a secondary alicyclic amine, such as dibutylamine, dibenzylamine, dicyclohexylamine, or mixed amines with an imine so as to introduce a primary amino group which can be reacted with an alkylene oxide followed by reaction with an imine and then the use of an alkylene oxide again. Similarly, one can start with a primary amine and introduce two moles of an alkylene oxide so as to have a compound comparable to ethyl diethanolamine and react with two moles of an imine and then with two moles of ethylene oxide.

Reactions involving the same reactants previously described, i. e., a suitable secondary monoamine plus an alkylene imine plus an alkylene oxide, or a suitable monoamine plus an alkylene oxide plus an alkylene imine and plus the second introduction or an alkylene oxide, can be applied to a variety of primary amines. In the case of primary amines one can either employ two moles of an alkylene oxide so as to convert both amino hydrogen atoms into an alkanol group, or the equivalent; or else the primary amine can be converted into a secondary amine by the alkylation reaction. In any event, One can obtain a series of primary amines and corresponding secondary amines which are characterized by the fact that such amines include groups having repetitious ether linkages and thus introduce a definite hydrophile etfect by virtue of the ether linkage. Suitable polyether amines susceptible to conversion in the manner described include those of the formula [R (O C "H2n)=]\ in which at is a small whole number having a value of l ormore, and maybe as much as 10 or 12; n is an integer having a value of 2 to 4, inclusive; m represents the numerall to 2; and m represents a number 0 to 1, with the proviso that the sum of in plus m equals 2; and R has its prior significance, particularly as a hydrocarbon radical. Other similar secondary monoamines equally suitable for such conversion reactions in order to yield appropriate secondary amines, are those of the composition as described in U. S. Patent No. 2,375,659, dated May 8, 1945, to Jones et al. In the above formula R may be methyl, ethyl, propyl, amyl, octyl, etc.

Other suitable secondary amines which can be converted into appropriate polyamines can be obtained from products which are sold in the open market, such as may be obtained by alkylation of cyclohexylmethylamine or the alkylation of similar primary amines, or for that matter, amines of the kind described in U. S. Patent No. 2,482,546, dated September 20, 1940, to Kaszuba, provided there is no negative group or halogen attached to the phenolic nucleus. Examples includes the following: beta phenoxyethylamine, gamma phenoxypropylamine, beta phenoxy alpha methylethylamine, and betaphenoxy-propylarnine.

Other secondary monoamines suitable for conversion into polyamines are the kind described in British Patent No. 456,517, and may be illustrated by In light of the various examples of polyamines which have been used for illustration it may be well to refer again to the fact that previously the amine was shown as Canon In the first of the'two above formulas if the reaction involves a terminal amino hydrogen obviously the radicals attached to the nitrogen atoms, which in turn combines with the methylene bridge, would be different than if the reaction took place at the intermediate secondary amino radical as diiferentiated from the terminal group. Again, referring to the second formula above, although a terminal amino radical is not involved it is obvious that one could obtain two difiierent structures for the radicals attached to the nitrogen atom united to the methylene bridge, depending on whehcr the reaction took place at either one of the two outer secondary amino groups, or at the central secondary amino group. If there are two points of reactivity towards formaldehyde as illustrated by the above examples it is obvious that one might get a mixture in which in part the reaction took place at one point and in part at another point. Indeed, there are well known suitable polyamine reactions where a large variety of compounds might be obtained due to such multiplicity of reactive radicals. This can be illustrated by the following formula:

Certain hydroxylated polyamines which may be employed and which illustrate the appropriate type of reactant used for the instant condensation reaction may be illustrated by the following additional examples:

\nn-om 14 As is well known one can prepare ether amino alcohols of the type RO-CH CH OH) NHCH CH NHCH CH (OH) CH --OR PART 4 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is diflicult to actually depict the final product of the .cogeneric mixture except in terms of the process itself.

Previous reference has been made to the fact that the procedure herein employed is comparable, in a general way, to that which corresponds to somewhat similar derivatives made either from phenols as differentiated from a resin, or in the manufacture of a phenol-amine-aldehyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557 in order to obtain a heatreactive resin. Since the condensation products obtained are not heat-convertible and since manufacture is not restricted to a single phase system, and since temperatures up to C. or thereabouts may be employed, it is obvious that the procedure becomes comparatively simple. Indeed, perhaps no description is necessary over and above what has been said previously, in light of subsequent examples. However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of these oogeneric mixtures is a resin pot of the kind de scribed in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt to be a fusible liquid at the early or low temperature stage of reaction if employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary room temperature. Thus, we have found it conevnient to use a solvent and particularly one which can be removed readily at a comparatively moderate temperature, for instance, at 150 C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can be conducted in such a way that the initial reaction, and perhaps the bulk of the reaction, takes place in a polyphase system. However, if desirable, one can use an oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively nonvolatile solvent such as-dioxane or the diethylether of ethyleneglycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the sense that it is not necessary to use an initial resin which is soluble only in any oxygenated solvent as just noted, and it is not necessary to have a single phase system for reaction.

Actually water is apt to be present as a solvent for the reason that in most cases aqueous formaldehyde is employed, which may be the commercial product which is approximately 37%, or it may be diluted down to about 30% formaldehyde. However, paraformaldehyde can be used 'but it is more difficult perhaps to add a solid material instead of the liquid solution and, everything else being equal, the latter is apt to be more economical. In any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction.

In the next succeeding paragraph it is pointed out that frequently it is convenient to eliminate all solvent, using a temperature of not over 150 C. and employing vacuum, if required. This applies, of course, only to those circumstances where it is desirable or necessary to remove the solvent. Petroleum solvents, aromatic solvent, etc., can be used. The selection of solvent, such as benzene, xylene, or the like, depends primarily on cost, i. e., the use of the most economical solvent and also on three other factors, two of which have been previously mentioned; (a) is the solvent to remain in the reaction mass without removal? (11) is the reaction mass to be subjected to further reaction in which the solvent, for instance, an alcohol, either low boiling or high boiling, might interfere as in the case of oxyalkylation?; and the third factor is this, is an effort to be made to purify the reaction mass by the usual procedure as, for example, a waterwash to remove any unreacted water-soluble polyamine, if employed and present after reaction? Such procedures are well known and, needless to say, certain solvents are more suitable than others. Everything else being equal, we have found xylene the most satisfactory solvent.

We have found no particular advantage in using a low temperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some other procedures that, in a general way, bear some similarity to the present procedure. There is no objection, of course, to giving the reaction an opportunity to proceed as far as it will at some low temperature, for instance, 30 to 40 but ultimately one must employ the higher temperature in order to obtain products of the kind herein described. If a lower temperature reaction is used initially the period is not critical, in fact, it may be anything from a few hours up to 24 hours. We have not found any case where it was necessary or even desirable to hold the low temperature stage for more than 3 or 4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there isa tendency for formaldehyde to be lost. Thus, if the reaction can be conducted at a lower temperature so as to use up part of the formaldehyde at such lower temperature, then the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is 'not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, thenagitation is required only to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but may be convenient under certain circumstances. On the other hand, if the products are not mutually soluble then agitation should be more vigorous for the reason that reaction probably takes place principally at the interfaces and the more vigorous the agitation the more interfacial area. The general procedure employed is invariably the same when adding the resin and the selected solvent, such as benzene or xylene. Refluxing should be long enough to insure that the resin added, preferably in a powdered form is completely soluble. However, if the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned U. S. Patent 2,499,368. After the resin is in complete solution the polyamine is added and stirred. Depending on the polyamine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehyde solution. If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible that the initial reaction mass could be a threenhase system instead of a two-phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction temperature or somewhat below, for example 35 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable form. For reasons pointed out we prefer to use a solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale manufacturing'there may be some advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss On a large scale if there is any difficulty with formaldehyde loss control, one can use a more dilute form of formaldehyde, for instance, a 30% solution. The reaction can be conducted in an autoclave and no attempt made to remove water until the reaction is over. Generally speaking, such a procedure is much less satisfactory for a number of reasons. For example, the reaction does not seem to go to completion, foaming takes place, and other mechanical or chemical difficulties are involved. We have found no advantage in using solid formaldehyde because even here water of reaction is formed.

Returning again to the preferred method of reaction and particularly from the standpoint of laboratory procedure employing a glass resin pot, when the reaction was proceeded as far as one can reasonably expect at a low temperature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C., for 4 or 5 hours, or at the most, up to 1024 hours, we then complete the reaction by raising the temperature up to 150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of polyamine or formaldehyde. At a higher temperature we use a phase-separating trap and subject the mixture to reflux condensation until the water of reaction and the Water of solution of the formaldehyde is eliminated. We then permit the temperature to rise to somewhere about C., and generally slightly above 100 C., and below C. by eliminating the solvent or part of the solvent so the reaction mass stays within this predetermined range. This period of heating and refluxing, after the water is eliminated, is continued until the reaction mass is homogeneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same way as the removal of solvents in resin manufacture described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary polyamine and 2 moles of formaldehyde. In some instances we have added a trace of caustic as an added catalyst but have found no particular advantage in this. In other cases we have used a slight excess of formaldehyde and, again, have not found any particular advantage in this. In other cases we have used a slight excess of amine, and again, have not found any particular advantage in so doing. Whenever feasible we have checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight, and particularly in some instances have checked whether or not the end-product showed surface-activity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted polyamine, if any is present, is another index.

17 In light of what has been said previously little more needs to be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration.

Example 1 b The phenol-aldehyde resin is the one that has been identified previously as Example 1a. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was completely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei as the value for n which excludes the 2 external nuclei, i. e., the resin was largely a mixture having 3 nuclei and 4 nuclei, excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

under 30 hours. In other examples it varied from 24 to more than 36 hours. The time can be reduced -by cutting the low temperature period to approximately 3 to 6 hours. Note that in Table II following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for a period of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solution and condensation. After all the water had been separated enough xylene was taken out to have the final product reflux for several hours somewhere in the range of 145 to 150 C., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the water, had been removed.

Note that as pointed out previously, this procedure is illustrated by 24 examples in Table II.

Table II Strength of Reac R'eac- Max. Ex. Resin Amt, Amine used and amount furmalde- Solvent used it-n tlon dtstill N 0. used grs. hyde s ln. and amt. temp time, temp.,

and amt. 0. hrs. C.

882 Amine A 296 g 30% 200 g. Xylene 500 g. 21-24 24 150 480 Amine A 148 g... g Xylene 480 g. 1 -23 27 156 633 Amine A 148 g. Xylene 610 g. 22-27 142 441 Amine B 176 g a Xylene 300 g. 20-25 28 1'46 480 Amine B 176 g Xylene 425 g. 23-27 f 34 150 633 Amino B 176 g Xylene 500 g. 25-27 a 152 882 Amine C 324 g. Xylene 625g 23-26 38 141 480 Amine G 162 g Xylene 315g... 20-21 25 143 633 Amine C 162 g Xylene 535 g. 23-24 25 140 473 Amine D 256 g..." Xylene 425 g. 22-25 25 148 511 Amine D 256 g Xylene 450 g 20-21 25 158 665 Amine D 256 g Xylene 525 g... 21-25 28 152 441 Amine E 208 g. Xylene 400 g. 22-24 26 143 480 Amine E 208 g. i Xylene 400 g 25-27; w 144 595 Amine E 208 g Xylene 500 g. 25-27 34 141 441 Amine F 236 g. Xylene 400 g. 21- 23 25 153 480 Amine F 235 g; Xylene 400 g. 20-22 28 i 150 511 Amine F 233 g Xylene 500 g 23-25 27 V 155 498 Amine G 172 g Xylene 400 g 20-21' 34 150 542 Amine G 172 g Xylene 450 g... 20-24 36 152 547 Amine H 221 g r. Xylene 500 g 20-22 30 1 48 441 Amine H 221 g, Xylene 400 g. 20-29 24 143 595 Amine I 172 g Xylene 450 g 20-22 32 151 391 Amine I 86 g Xylene 300 g. 20-26 36 147 882 grams of the resin identified as 1a preceding were powdered and mixed with a considerably lesser weight of xylene, to wit, 500 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximately 33 to 38 C., and 296 grams of symmetrical di(hydroxyethyl) ethylenediamine were added; The mixture was stirred vigorously and formaldehyde used was a 30% solution and the amount employed was 200 grams. It was added in a little over 3 hours. The

mixture was stirred vigorously and kept within a temperature range of 33 to 48 C. for about 17 hours. At the end of this time it was refluxed using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time. The presence of formaldehyde was noted. Any unreacted formaldehyde seemed to disappear Within about 3 hours or thereabouts. As soon as the odor of formaldehyde was no longer particularly noticeable or detectible the phase-separating trap was set so as to eliminate part of the xylene was removed until the temperature reached approximately 150 C. or perhaps a little higher. The reaction mass was kept at this temperature for a little over 4 hours and the reaction stopped. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of. the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to re move the excess xylene. The residual material was dark red in color and had the consistency of a sticky fluid or tacky resin. The overall-time for reaction was somewhat As to the formulas of the above amines referred to as Amine A through Amine I, inclusive, see immediately following:

Amlne G HO CHaCHsNH-CHaCHOHCHs-NHCHICHiQH HOCHsCHzNH-OHs Ho cmomNa-crr HO ornomNa-om ..able conditions without any catalyst at all.

Employing polyepoxides in combination with a nonbasic reactant the usual catalysts include alkaline materials such as caustic soda, caustic potash, sodium methjylate, etc. are of the kind characterized by iron and tin chloride. Furthermore, insoluble catalysts such as clays or specially Other catalysts may be acidic in nature and prepared mineral catalysts have been used. If for any reason the reaction did not proceed rapidly enough with the diglycidyl ether or other analogous reactants, then a'small amount of finely divided caustic soda or sodium methylate could be employed as a catalyst. The amount generally employed would be 1% or 2%.

It goes without saying that the reaction can take place in an inert solvent, i. e., one that is not oxyalkylationsusceptible. Generally speaking, this is most conveniently an aromatic solvent such as xylene or a higher boiling coal tar solvent, or else a similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenated solvent such as thediethylether of ethylene glycol, or the diethylether or propyleneglycol, or similar ethcrs,-eith'er alone or in combination with a hydrocarbon solvent. The selection of the solvent depends in part on the subsequent use of the derivatives or reaction prod- Example 1c The product was obtained by reaction between the diepoxide previously designated as diepoxide A, and condensate 2b. Condensate 2b was derived from resin 3a.

was added during approximately an hours time.

Resin 3a, in turn, was obtained from the tertiary amylphenol and formaldehyde. Condensate 2b employed as reactants resin 3a and diethanolamine. The amount of resin employed was 480 grams; the amount of diethanolamine employed was grams, and the amount of 37% formaldehyde employed was 81 grams. The amount of solvent (xylene) employed was 450 grams. All this has been described previously.

The solution of the condensate in xylene was adjusted to a 50% solution. In this particular instance, and in 'practically all the others which appear in the subsequent tables, the examples are characterized by. the factthat no alkaline catalyst was added. The reason is, of course, that the condensate as such is strongly basic. If desired, a small amount of an alkaline catalyst could be added, such as finely powdered caustic soda, sodium methylate, etc. If such alkaline catalyst is added it may speed up the reaction but it may also cause an undesirable reaction, such as the polymerization of the diepoxide.

In any event, 128 grams of the condensate dissolved in approximately an equal weight of xylene were stirred and heated to about 105 C. 18.5 grams of the diepoxide previously identified as diepoxide A, and dissolved in an equal weight of xylene, were added dropwise. The initial addition of the xylene solution carried the temperature to about 107 C. The remainder of the diepoxide During this period of time the reflux temperature rose to about 122 C. The product was allowed to reflux at a temperature in the neighborhood of C. using a phase-separating trap. A small amount of xylene was removed by means of the phase-separating trap so that the temperature rose gradually to a maximum of 180 C. The mixture was refluxed at 180 C. for approximately 3%. hours. Experience has indicated that this period of time was sufficient tocomplete the reaction.

At the end of the period the xylene which had been removed during the reflux period was returned to the mixture. A small amount of material was withdrawn and the xylene evaporated on a hot plate in order to examine the physical properties. The material was a dark red viscous semi-solid. It was insoluble in water, it was insoluble in 5% gluconic acid, and it was soluble in xylene, and particularly in a mixture of 80% xylene and 20% methanol. However, if the material was dissolved in an oxygenated solvent and then shaken with 5% gluconic acid it showed a definite tendency to disperse, suspend, or form a sol, and particularly in a xylene-methanol mixed solvent as previously described, with or without the further addition of a little acetone.

The procedure employed of course is simple in light of what has been said previously and in effect is a procedure similar to that employed in the use of glycide or methylglycide as oxyalkylating agents. See, for example, part 1 of U. S. Patent No. 2,602,062 dated July 1, 1952, to De Groote.

Various examples obtained in substantially the same manner are enumerated in the following tables:

Table III Con- Dm} Time M Ex. den- Amt., 0nd 9 Amt, Xylene. Molar of reac- No. Eggs grs. used grs. grs. ratio tlion, c Color and physlcal state 1%: i i i 180 Darllgviscous semi-solid.

. 182 0. 123 A 18. 5 141. 5 2:1 4 186 Do. 4e 130 A 18. 5 148. 5 2:1 4 184 Do. 5a.--- 10b 148 A 18.5 166.5 2:1 4.5 185 Do. 60..... 12b 187 A 18.5 205.5 2:1 4.5 188 Do. 70..... 1317.----- 132 A 18.5 150.5 2:1 4.5 180 D0. 80..... 18b 152 A 18.5 170.5 2:1 4.5 182 Do. 9c-.- 19b 137 A 18.5 154.5 2:1 4.5 180 D0. 1%.... 20b A 18.5 1635 2:1 4.5 D0.

Table IV 0011- Time Ex. den- Amt., g fig Amt Xylene, Molar of reacggg' N o. sate grs. used grs. grs. ratio tion, C Color and physical state used hrs.

1d 211---... 1'28 B 11 139 2:1 4 180 Dark viscous semi-solid;

d 134 B 11 145 2: 1 4 178- D0. 123 B 11 134' 2:1 4 175 D0. 130 B 11 141 2:1 4 182 D0. 148 B 11 159 2: 1 4 178 D0. 187 B 11 198 2: 1 5 182 Do. 132 B 11 143 2: 1 4. 5- 180 Do. 152 B 11 163 2:1 5 175 Do. 136 B 11 147 2:1 5= 182 D0. 145 B 11' 156 2:1- 5 180 D0.

Solubility in regard to all these compounds was substantially similar to that which was described in Example 1c.

Table V Probable Resin con- 3 235 3 Amt. of Amt. of number of Ex. No. densalte rea'cflo'n product, solvent, hydroxlyls use grs. grs. per mo 0- product Gule Table VI Probable Resin congf lgg g Amt. of Amt; of number of Ex. No. dons-(lite i product, solvent, hydroxfls use grs. grs. per mo eproduct cule times. we have found a tendency for an insoluble mass to form. or atleast to obtain incipient cross-linking or gelling even when the molal ratio is in the order of 2 moles of resin to one of diepoxide. We have found this can be avoided by any one of the following procedures or their equivalent. Dilute the resin or the diepoxide, or both, with an inert solvent, such. as xylene or the like. In some instances an oxygenated. solvent, such as the diethyl ether of ethyleneglycol may he employed. Another procedure which is helpful is to reduce the amount of catalyst used, orv reduce the temperature'of reaction by adding a small amount of initially lower boiling solvent such as benzene, or use benzene entirely. Also, we have found it desirable at times to use slightly less than apparently the theoretical amount of diepo-xide, for instance 90% or 95% instead of 100%. The reason for this fact may reside in the possibility that the molecular weight dimensions on either the resin molecule or the diepoxide molecule may actually vary from the true molecular weight by several percent.

Previously the condensate has been depicted in a simplified form which, for convenience, may be shown thus:

(Amine)CH (Resin) CH (Amine)- Following such simplification the reaction product with a polyepoxide and particularly a diepoxide, would be indicated thus:

[(Amlne) CHflResin) OH (Amlne)]' [D. G. E.]

[(Amine) CH2 (Resin) CH2 (Amine)1 in which D. G. E. represents adiglycidyl other as specified. If the amine happened to have more than one reactive hydrogen, as in the case of a hydroxylated amine or polyamine, having amultiplicity of secondary amino groups it is obvious that other side reactions could take place as. indicated by the following, formulas:

[(Amine) OHg(Amine)] to; o. E.]'-

[.(Amine) CH2 (Amlne)] [("Resin).CHa(Resin)] ID; G. E.]

[(Resin) CH(Resin)] [(AmluelCHr (Amine)] [D. G. E.]

[(Resln)] All the above indicates the complexity of the reaction product obtained after treating the amine-modified resin condensate with a polyepoxide and particularly diepoxide as herein described.

PART 6 The preparation of the compounds or products described in Part 5, preceding, involves an oxyalkylating agent, to wit, a polyepoxide and usually a diepoxide. The procedure described in the present part is a further oxyalkylationstep but involves the use of a monoepoxide or the equivalent. The principal difference is only that while polyepoxides are invariably nonvolatile and can be reacted under a condenser, at least numerous monoepoxides and particularly ethylene oxide, propylene oxide, butylene oxide, etc., involve somewhat different operating conditions. Glycide and methylglycide react under practically the same conditions as the polyepoxides. Actually, for purpose of convenience,.it is most desirable to conduct the previous reaction, i. e.,. the one involving the polyepoxide, in equipment such that subsequent reaction With monoepoxides may follow without interruption. For this reason considerable is said in detail as to oxyethylation, etc.

Although ethylene oxide and propylene oxide may represent. less of a: hazard" than glycide, yet these reactants should be handled with extreme. care. One suitable procedure involves the. use of propylene oxide or butylene oxide as a solvent as well as a reactant in the earlier stages along with ethylene oxide, for instance, by dissolving the appropriate resin. condensate in propylene oxide. even though oxyalkylation is taking, place to a greater or lesser degree. After a solution has been obtained which represents the selected resin condensate dissolved in propylene oxide or butylene oxide, or a mixture which includes. the oxyalkylated product, ethyl ene oxide: is added to react with the liquid mass until hydrophile properties are obtained, if not previously present to the desired degree. Indeed, hydrophile character can be reduced or balanced by use of some other oxide, such as propylene oxide or butylene oxide. Since ethylene oxide is more reactive than propylene oxide or butylene oxide, the final product may contain some unreacted propylene oxide or butylene oxide which can be eliminated by volatilization or distillation in any suitable manner. See article entitled Ethylene Oxide Hazards and Methods of Handling, Industrial and Engineering Chemistry, volume 42, No. 6, June 1950, pp. 1251-1258. Other procedures can be employed as, for example, that described in U. S. Patent No. 2,586,767, dated February 19, 1952, to Wilson.

The amount of monoepoxides employed maybe as high as.50 parts of monoepoxide for one part of monoepoxide treated amine-modified phenol-aldehyde condensation product. I

p Example 1D The polyepoxide-derived oxyalkylation-susceptible compound is the one previously designated as 1c. Polyepoxide-derived condensate 10 was obtained, in turn, from condensate 2b and diepoxide A. Reference to Table II shows the composition of condensate 2b. Table II shows it was obtained from resin 5a, amine A and formaldehyde. Amine A is symmetrical di(hydroxyethyl) ethylene diamine. Table I shows that resin 5a was obtained from tertiary amylphenol and formaldehyde.

For purpose of convenience, reference herein and in the tables to the oxyalkylation-susceptible compound will be abbreviated. in the table heading as OSC; reference is to the solvent-free material since, for convenience, the amount of solvent is noted in a second column. Actually, part of the solvent may have been present and in practically every case was present in either the resinification process or the condensation process, or in treatment with a polyepoxide. In any event, the amount of solvent present at the time of treatment with a monoepoxide is indicated, as stated, on a solvent-free basis.

14.65 pounds of the Polyepoxide-derived condensate were mixed with 14.65 pounds of solvent (xylene in this series), along with one pound of finely powdered caustic soda as a catalyst. The reaction mixture was treated with 4.75 pounds of ethylene oxide. At the end of the reaction period the molal ratio of oxide to initial compound was approximately 14.65 to one, and the theoretical molecular weight was approximately 3880.

Adjustment was made in the autoclave to operate at a temperature of about 125 C. to 130 C., and at a pres sure of to pounds per square inch.

The time regulator was set so as to inject the oxide in approximately A: hour and then continue stirring for a half hour longer, simply as a precaution to insure complete reaction. The reaction went readily and, as a matter of fact, the ethylene oxide probably could have been injected in 30 minutes instead of an hour and the subsequent time allowed to insure completion of reaction may have been entirely unnecessary. The speed of reaction, particularly at low pressure, undoubtedly was due in a large measure to the excellent agitation and also to the comparatively high concentration of catalyst.

A comparatively small sample, less than 50 grams, was withdrawn merely for examination as far as solubility or emulsifying power was concerned, and also for the purpose of making some tests on various oil field emulsions. The amount withdrawn was so small that no cognizance of this fact is included in the data or subsequent data, or in data reported in tabular form in subsequent Tables VII, VIII and IX.

The size of the autoclave employed was 35 gallons. In innumerable oxalkylations we have withdrawn a substantial portion at the end of each step and continued oxyalkylation on a partial residual sample. This was not the case in this particular series. Certain examples were duplicated as hereinafter noted and subjected to oxyalkylation with a different oxide.

Example 2D This simply illustrates further oxyalkylation of Example 1D, preceding. The oxyalkylation-susceptible compound lc is the same as the one used in Example 1D, preceding, because it is merely a continuation. In subsequent tables, such as Table VII, the oxyalkylation-susceptible compound in the horizontal line concerned with Example 2D refers to oxyalkylation-susceptible compound 10. Actually, one could refer just as properly to Example ID at this stage. It is immaterial which designation is used so long as it is understood such practice is used consistently throughout the tables. In any event, the amount of ethylene oxide introduced was less than previously, to wit, only 4.75 pounds. This meant the amount of oxide at the end of the stage was 9.50 pounds, and the ratio of oxide to oxyalkylation-susceptible compound (molar basis) at the end was 43.2 to 1. The theoretical molecular weight was 4830. There was no added solvent. In other words, it remained the same, that is, 14.65 pounds and there was no added catalyst. The entire procedure was substantially the same as in Example 1D, preceding.

In this, and in all succeeding examples, the time and pressure were the same as previously, to wit, C. to C., and the pressure 10 to 15 pounds. The time element was only one-half hour because considerably less oxide was added.

Example 3D The oxyalkylation proceeded in the same manner as in Examples 1D and 2D. There was no added solvent and no added catalyst. The amount of oxide added was 4.75 pounds. The total amount of oxide at the end of the stage was 14.25 pounds. The molal ratio of oxide to condensate was 65 to' 1. The theoretical molecular weight was approximately 5800, and as previously noted the temperature and pressure were the same as in preceding Example 2D, but the time period was 45 minutes.

Example 4D The oxyalkylation was continued and the amount of oxide added was the same as before, to wit, 4.75 pounds. The amount of oxide added at the end of the reaction was 19.0 pounds. There was no added solvent and no added catalyst. Conditions as far as temperature and pressure are concerned were the same as in previous examples. The time period was the same as before, to wit, 45 minutes. The reaction at this point showed modest, if any, tendency to slow up. The molal ratio of oxide to oxyalkylation-susceptible compound was 86.4 to 1. The theoreticalmolecular weight was 6730.

Example 5D The oxyalkylation was continued with the introduction of 9.5 pounds of oxide. No added solvent was introduced and likewise no added catalyst was introduced. The theoretical molecular weight at the end of the reaction was approximately 8630. The molal ratio of oxide to oxyalkylation-susceptible compound was 130 to l. The time period was considerably longer, to wit, 2 hours.

Example 6D The same procedure was followed as in the previous examples without the addition of either more catalyst or more solvent. The amount of oxide added was the same as before, to wit, 28.5 pounds. The amount of oxide at the end of the reaction was considerable, 57.0 pounds. The time required to complete the reaction was greater than previously, to wit, 5 hours. At the end of the reaction period the ratio of oxide to oxyalkylationsusceptible compound was 260 to 1, and the theoretical molecular weight was 14,300.

The same procedure as described in the previous examples was employed in connection with a number of the other condensations described previously. All these data have been presented in tabular form in Tables VII through XII.

In substantially every case a. 35-gallon autoclave, was employed, although in some instances the initial oxyethylation was started in a 15-gallon autoclave and then transferred to a ZS-gallon autoclave, or at times to the 35-gallon autoclave. This is immaterial but happened to be a matter of convenience only. The solvent used in all cases was xylene. The catalyst used was finely powdered' caustic soda,

Referring to Tables VII, VIII and IX, it will be noted that compounds 1D through 18D were obtained by the use of ethylene oxide, whereas Examples 19D through 36D were obtained by the use of propylene oxide; and Examples 37D through 54D were obtained by the use of butylene oxide.

Referringnow to Table VIII specifically, it will be noted that the series of examples beginning with 113 were obtained, in turn, by use of both ethylene and propylene oxides, using ethylene first; in fact, using Example 4D as the oxyalkylation-susceptible compound. This applies to series 1E through 18E.

Similarly, series 19E through 36E involve the use of both propylene oxide and ethylene oxide in which the propylene oxide was used first, to wit, 19E was prepared from 24D, a compound which was initially derived by use of propylene oxide.

Similarly, Examples 37E through 54E.involve the use of ethylene oxide and butylene oxide, the ethylene oxide being used first. Also, these two oxides were used in the series 55E through 72E, but in this latter instance the butylene oxide was used first and then the ethylene oxide.

Series 73E through 90E involve the use of propylene oxide and butylene oxide, butylene oxide being used first and propylene oxide being used next.

In series 1F through 18F the three oxides were used; It will be noted in Example IF the initial compound was 76E, Example 76E, in turn, was obtained from a compound in which butylene oxide was used initially and then propylene oxide. Thus, the oxide added in the series 1F through 6F was by use of ethylene oxide as indicated in Table IX.

Referring to Table IX, in regard to Example 19F it will be noted again that the three oxides were used and 19F was obtained from 60E. Example 60E, in turn, was obtained by using butylene oxide first and then ethylene oxide. In Example 19F and subsequent examples, such as 20F, 21F, etc. propylene oxide was added.

Tables X, XI and XII give the data in regard to the oxyalkylation procedure as far as temperature and pres sure are concerned and also give some data as to'solubility of the oxyalkylated derivative in water, xylene and kerosene.

Referringto Table VII in greater detail, the data are as follows: The first column gives the example numbers, such as 1D, 2D, 3D, etc. etc.; the second column gives the oxyalkylation-susceptible compound employed which, as previously noted in the series 1D through 6D, is Example 1C, although it would be just as proper to say that in the case of 2D the oxyalkylation-susceptible compound was 2D. Actually, reference is to the parent de- 7 rivative for the reason that the figure stands constant and probably leads to a more convenient presentation. Thus, the third column indicates the epoxide-derived condensate previously referred to.

The fourth column shows the amount of ethylene oxide in the mixture prior to the particular 'oxyethylation step. In the case of Example 1D there is no oxide used but it appears, of course, in 2D, 3D, and 4D, etc.

The fifth column can be ignored for the reason that it is concerned with propylene oxide only, and the sixth column can be ignored for the reason that it is concerned with butylene oxide only.

The seventh column shows the catalyst which is invariably powdered caustic soda,

The eighth column shows the amount of solvent which isxylene unless otherwise stated.

The ninth column shows the oxyalkylation-susceptible compound which in this series is the polyepoxide-derived condensate.

The'tenth column shows the amount of ethylene oxide in at the end of the particular step.

Column eleven shows the same data for propylene oxide and column twelve shows data for butylene oxide. For obvious reasons these can be ignored in the series 1D through 18D.

Column thirteen shows the amount of the catalyst at the end of the oxyalkylation step, and column fourteen shows the solvent at the end of the oxyalkylation step.

The fifteenth, sixteenth and seventeenth columns are concerned with molal ratio of the individual oxides to the oxyalkylation-susceptible compound. Data appears only in column fifteen for the reason, previously noted, that no butylene or propylene oxide were used in the present instance.

The theoretical molecular weight appears at the end of the table which is on the assumption, as previously noted, as to the probable molecular weight of the initial compound, and on the assumption that all oxide added during the period combined. This is susceptible to limitations that have been pointed out elsewhere, particularly in the patent literature.

Referring now to the second series of compounds in Table VII, to wit, Examples 19D through 36D, the situation is the same except that it is obvious that the oxyalkylating agent used was propylene oxide and not ethylene oxide. Thus the fourth column becomes a blank and the tenth column becomes a blank and the fifteenth column becomes a blank, but column five, which previously was a blank in Table VH, Examples 1D through 18D, now carries data as to the amount of propylene oxide present at the beginning of the reaction. Column eleven carries data as to the amount of propylene oxide present at the end of the reaction, and column sixteen carries data as to the ratio of propylene oxide to the oxyalkylation-susceptible compound. In all other instances the various headings have the same significance as previously.

Similarly, referring to Example 37D through 54D in Table VII, columns four and five are blanks, columns ten and elevent are blanks, and columns fifteen and sixteen are blanks, but data appear in column six as to butylene oxide present before the particular oxyalkylation step. 'Column twelve gives the amount of butylene oxide present at the end of the step, and column seventeen gives the ratio of butylene oxide to oxyalkylation-susceptible compound.

Table VIII is in essence the data presented in exactly the same way except the two oxides appear, to wit, ethylene oxide and propylene oxide. This means that there are only three columns in which data does not appear, all three being concerned with the use of butylene oxide. Furthermore, it shows which oxide was used first by the very fact that reference to Example 1E, in turn, refers to 2D, and also shows that ethylene oxide was present at the very first stage. Furthermore, for ease of comparison and also to be consistent, the data under molal ratio in regard to ethylene oxide and propylene oxide goes back to the original diepoxide-derived condensate 1c. This is obvious, of course, because the figures 86.4 and 5 0.5 coincide with the figures for 4D derived from 1c as shown in Table VII.

In Table VIII (Examples 19E through 36E) the same situation is involved except, of course, propylene oxide is used first and this, again, is perfectly apparent. Three columns only are blank, to wit, the three referring to butylene oxide. The same situation applies in examples such as 37B and subsequent examples where 27 the two oxides used are ethylene oxide and butylene oxide, and the table makes it plain that ethylene oxide was used first. Inversely, Example 55B and subsequent examples show the use of the same two oxides but with butylene oxide being used first as shown on the table.

Example 73E and subsequent examples relate to the use of propylene oxide and butylene oxide. Examples beginning with IE, Table IX, particularly 2F, 3F, etc., show the use of all three oxides so there are no blanks as in thefirst step of each stage where one oxide is missing. It is not believed any further explanation need be offered in regard to Table IX.

As previously pointed out certain initial runs using one oxide only, or in some instances two oxides, had to be duplicated when used subsequently for further reaction. It would be confusing to refer to too much detail in these various tables for the reason that all the data appear in considerable detail and is such that all results can be readily shown.

Reference to solvent and amount of alkali at any point takes into consideration the solvent from the previous step and the alkali left from this step. As previously pointed out, Tables X, XI and XII give operating data in connection with the entire series, comparable to what has been said in regard to Examples 1D through 6D.

The products resulting from these procedures may contain modest amounts, or have small amounts, ofthe sol vents as indicated by the figures in the tables. If desired, the solvent maybe removed by distillation, and particularly vacuum distillation. Such distillation also may remove traces or small amounts of uncombined oxide, if present and volatile under the conditions employed.

Obviously, in the use of ethylene oxide and propylene oxide in combination one need not first use one oxide and then the other, but one can mix the two oxides and thus obtain what may be termed an indifferent oxyalkylation, i. e., not attempt to selectively add one and then the other, or any other variant.

Needless to say, one could start with ethylene oxide and then use propylene oxide, and then go back to ethylene oxide; or, inversely, start with propylene oxide, then use ethylene oxide, and then go back to propylene oxide; or, one could use a combination in which butylene oxide is used along with either one of the two oxides, just mentioned, or a combination of both of them.

The same would be true in regard to a mixture of ethylene oxide and butylene oxide, or butylene oxide and propylene oxide.

The colors of the products usually vary from a reddish amber tint to a definitely red, and amber, or a straw color, or even a pale straw color. The reason is pri- Table VII Composition before Composition at end E Oxides Oxides Molal ratio x. No. SC, Cata- Sol- Cata- Sol- Theo.

ex. 050, lyst, vent, 0S0, lyst, vent, EtO PrO BuO mol. N0. lbs. EtO, PrO, BuO, lbs. lbs. lbs. EtO, PrO, 13110, lbs. lbs. to my to oxyto oxywt.

lbs. lbs. lbs. lbs. lbs. lbs. alkyl alkyl. alkyl.

suscept. suscept. suscept. compd. compd. compd.

14.65 1. 0 14. 65 14.65 4. 75 1.0 14.65 21. 6 3, 880 14. 65 1. 0 14. 65 14.65 9. 50 1. 0 14. 65 43. 2 4, 830 14.65 1.0 14. 65 14. 65 14.25 1. 0 14.65 5, 780 14. 65 1.0 14.65 14. 65 19.0 1.0 14.65 6,730 14. 65 1.0 14.65 14.65 28. 5 1.0 14.65 8, 630 14.65 1.0 14.65 14. 65 57. 0 1.0 14.65 14, 330 15. 25 1.0 15.25 15.25 5. 1 1.0 15. 25 4,070 15. 25 1. 0 15. 25 15. 25 10. 2 1. 0 15. 25 5, 090 15.25 1.0 15.25 15.25 15.3 1.0 15.25 6,110 15.25 1. 0 15.25 15.25 30. 6 1.0 15. 25 9, 170 15.25 1.0 15.25 15.25 45.9 1.0 15.25 12, 230 15.25 1. 0 15.25 15. 25 61.2 1. 0 15.25 15, 290 14. 1.0 14. 15 14.15 4. 7 1.0 14. 15 3, 770 14. 15 1. D 14. 15 14. 15 9. 4 1. 0 14. 15 4, 710 14. 15 1.0 14.15 14.15 14. 1 1.0 14. 15 5, 650 14. 15 1. 0 14.15 14. 15 28. 2 1. 0 14. 15 8, 470 14.15 1.0 14. 15 14. 15 37. 6 1.0 14.15 10, 350 14. 15 1.0 14. 15 14.15 56. 4 1.0 14. 15 14, 110 14.65 1. 5 14.65 14.65 1. 5 14.65 5,860 14. 65 1. 5 14. 65 14. 65 29. 1. 5 14. 65 8, 790 14.65 1.5 14.65 14.65 1. 5 14.65 11, 720 14. 65 1. 5 14. 65 14. 65 58. 6 1. 5 14. 65 14, 650 14. 65 1. 5 14. 65 14. 65 73. 2 1. 5 14. 65 17, 580 14. 65 1. 5 14.65 14.65 117. 2 1. 5 14.65 26, 370 15. 1. 5 15.25 15.25 15. 2 1. 5 15.25 6,100 15.25 15. 25 1. 5 '15. 25 15. 25 30. 5 1. 5 15.25 9,150 15. 25 30. 5 1. .5 15.25 15. 25 45. 75 1. 5 15. 25 12,200 15.25 45. 75 1. 5 15.25 15.25 61.0 1. 5 15.25 15,250 15.25 61.0 1. 5 15. 25 15.25 76. 25 1. 5 15.25 18, 300 15.25 76.25 1. 5 15.25 15.25 91. 5 1. 5 15.25 21, 350 14.15 1. 5 14. 15 14.15 14.15 1. 5 14. 15 5, 660 14. 15 14. 15 1. 5 14. 15 14. 15 28. 3 1. 5 14. 15 8, 490 14.15 28.3 1. 5 14.15 14. 15 42. 1. 5 14. 15 11,320 14.15 42. 45 1. 5 14. 15 14. 15 56. 6 1. 5 14. 15 14,150 14.15 56. 6 1. 5 14.15 14. 15 84. 9 1. 5 14. 15 810 14.15 84. 9 1. 5 14. 15 14. 15 99. 05 1. 5 14. 15 22, 640 14. 1. 0 14. 65 14. 65 5. 0 1.0 14. 65 13. 9 .930 14. 65 5. 0 1. 0 14. 65 14. 65 10. 0 1.0 14. 65 27. 8 4, 930 14.65 10.0 1.0 14. 65 14.65 15. O 1.0 14.65 41. 7 5, 930 14.65 15.0 1. O 14.65 14.65 30. 0 1.0 14. 65 83. 4 8, 930 14. 65 30. 0 1. 0 14. 65 14. 65 40. 0 1.0 14. 65 111. 2 10, 930 14. 65 40. 0 1. 0 14. 65 14. 65 60. 0 1. 0 14. 65 166. 8 14, 930 15.25 1.0 15.25 15. 25 5. 25 l. 0 15. 25 14.6 4, 15.25 5. 25 1.0 15.25 15. 25 10.5 1. 0 15.25 29. 2 5, 15.25 10. 5 1.0 15.25 15.25 21. 0 1.0 15.25 58. 4 7, 250 15.25 21. 0 1.0 15.25 15. 25 31. 5 1. 0 15. 25 87. 6 9, 350 15.25 31. 5 1.0 15.25 15. 25 42. 0 1.0 15.25 116. 8 11, 450 15.25 42.0 1.0 15.25 15. 25 63.0 1. 0 15.25 175. 2 15, 650 14. 15 1.0 14.15 14. 15 4. 5 1. 0 14.15 12. 5 3, 730 14. 15 4. 5 1.0 14. 15 14.15 9. 0 1. 0 14. 15 25.0 4, 630 '14. 15 9. 0 1.0 14. 15 14. 15 18.0 1. 0 14. 15 50. O 6, 430 14.15 18.0 1.0 14. 15 14. 15 27.0 1.0 14. 15 75.0 8, 230 14.15 27. 0 1.0 14. 15 14. 15 36.0 1.0 14. 15 100.0 10,030 14. 15 36. 0 1. 0 14. 15 14. 15 63. 0 1. 0 14. 15 175.0 15, 430

Theo. mol. wt.

Molai ratio EtO to oxyto oxy to oxy- .a1kyi. alkyl. alkyl suscept. suscept. suscep compd. compd; compd.

444444222222222222628468246.82648264222222244 nmfifinmflnmnmnmumnmom 14 sd drmLaminmbwlaHuuml iLliflwoaLqunmnmnwnmqmom 111111 11 11 11222 S01- vent, lbs.

Catalyst,

8 7 2 555555555555 5 5H55H55 5 5555 5 55 5555 55555555 5555555555555 555555555555555555555555 6nn6666222222wMH1H166666622222211111166666622 1111666666222 2211111120665620222.vfivZZllllHF k4m1444.5555554444444444445555.5544454444444455 444444 444444555555444444444444555555444444 111111111111111111111111111111111111111111111 111111111111111111111111111111111111111111 5555555555555555555555555555555555 0500000000000000000000000000000000000055555555555555.0555 LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL Composition at end lbs.

5 000011 239876430000003333333333330000 0222222 "06 nmlw diolzndflzuau 123566666666665666666653333 3444 444 33%% Oxides EtO, PrO,

Table VIII 55555555555555 555555555555555555555555555555555555555555555555555 5555 3555555555555555 66666622222211wwmm666666222222111111666666222222111111666666222222111 11666666222222111111 oso,

. [1411111154155551111111114;4m5.99maaililiiiliiiiassaii o mmmnnmwmmmmwmlmmnmmmmmnullllllnmmml1111111111111111111111111111111111111111111111111MMMMM S01- vent, lbs.

555555555555 555555555555555555 55555555555555555555555555555555555555555555555555 6666662znaz zzwmwmwwfifififi66222222111111666666222229.11111166666622222211111166666622222211wmww 5 55 55555544444444 4444 5555554 444444444445555554444444444 44555555 MMMMMM1wllmmmnmmmMMMMMMM111111111111111111111111111111111111111111111111111111111111MMMMMM I Gata- I lyst,

5 05555555555555555555 55 5555555555555000000000000000000000000000000000000555555555555555555 LLLLLLLLLLLLLLLLLLLLLLLKLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL.LLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLLL BuO, lbs. 7 lbs.

Oxides PrO, lbs.

v i 5 5 .v I 55 134692222225555550000' I 6 77777711111199.9979 M$Q5M11111199999999999 111111 Composition before Cam 00000056666611.1111 75205 12468 74100200000022.2222 0 m HNNHNNWWWWWWMMMMMM MNE m NW3d. 1 1255555 666666555555 1 lbs.

Table IX Composition before Oomposltlon at end E Oxides Oxides Molal ratio x. No. 080, Oata- Sol- Cata- Sol- Theo.

ex. 080, lyst, vent, S0, lyst, vent, EtO PrO BuO me]. No. lbs. Et PrO, BuO, lbs. lbs. lbs. EtO, PrO, BuO, lbs. lbs. to oxyto oxyto oxywt.

lbs. lbs. lbs. lbs. lbs. lbs. alkyl. alkyl. alkyl.

suscept. suscept. suscept. compd. compd. compd.

1F--- 76E 14 65 58.6 30.0 1.5 14.65 14. 65 4.75 58.6 30.0 1.5 14.65 21.6 202.0 111.2 21,600 2F-.- 76E- 14. 65 4.75 58.6 30.0 1.5 14.65 14.65 9. 50 58.6 30.0 1.5 14. 65 43.2 202.0 111.2 22,550 3F 76E--- 14. 65 9.50 58.6 30.0 1.5 14.65 14. 65 14.25 58.6 30.0 1.5 14. 65 64.8 202.0 111.2 23, 500 4 76E--- 14 65 14.25 58.6 30.0 1.5 14. 65 14. 65 19.0 58.6 30.0 1.5 14. 65 86.4 202.0 111.2 24,450 5F--- 76E.-- 14. 65 19.0 58.6 30.0 1.5 14. 65 14. 65 23.75 58.6 30.0 1.5 14. 65 108.0 202.0 111.2 25,400 6F 76E 14. 65 23.75 58.6 30.0 1.5 14. 65 14. 65 28.50 58.6 30.0 1.5 14.65 129.6 202.0 111.2 26,350 7F-.- 82 15. 25 61.0 42.0 1.5 15. 25 15. 25 5.1 61.0 42.0 1.5 15.25 23.2 210.4 116.8 24,690 SF... 82E 15.25 5.1 61.0 42.0 1.5 15. 25 15.25 10.2 61.0 42.0 1.5 15. 25 46.4 210.4 116.8 25,730 9F 82E-- 15. 25 10.2 61.0 42.0 1.5 15. 25 15. 25 15.3 61.0 42.0 1.5 15. 25 69.6 210.4 116.8 26,770 10F 82E.-- 15.25 15.3 61.0 42.0 1.5 15.25 15.25 20.4 01.0 42.0 1.5 15.25 92.8 210.4 116.8 27,810 11F 82E 15.25 20.4 61.0 42.0 1.5 15.25 15.25 25.5 61.0 42.0 1.5 15.25 116.0 210.4 116.8 28,850 12F. 82 15. 25 25.5 61.0 42.0 1.5 15. 25 15. 25 30.6 61.0 42.0 1.5 15. 25 139.2 210.4 116.8 29,890 13E. 89E 14.15 70. 75 36.0 1.5 14.15 14.15 4.7 70. 75 36.0 1.5 14.15 21.4 292.8 100.0 25,120 14F 89 14.15 4.7 70.75 36.0 1.5 14.15 14.15 9.4 70.75 36.0 1.5 14.15 42.8 292.8 100.0 26.060 15F. 89E--- 14.15 9.4 70. 75 36.0 1.5 14.15 14.15 14.1 70. 75 36.0 1.5 14.15 64.2 292.8 100.0 27,000 16F. 89E--- 14.15 14.1 70. 75 36.0 1.5 14.15 14.15 18.8 70. 75 36.0 1.5 14.15 85.6 292.8 100.0 27,940 17 89E 14.15 18.8 70. 75 36.0 1.5 14.15 14.15 23.5 70. 75 36.0 1.5 14.15 107.0 292.8 100.0 28,880 18F 89E--- 14.15 23.5 70. 75 36.0 1.5 14.15 14.15 28.2 70. 75 36.0 1.5 14.15 128.4 292.8 100.0 20,820 19F.- 60 0- 14. 65 28.5 60.0 1.5 14. 65 14. 65 28.5 7.25 60.0 1.5 14. 65 129.6 25.0 166.8 22,080 20F E.- 14. 28.5 7.25 60.0 1.5 14. 65 14. 65 28.5 14.50 60.0 1.5 14. 65 129.6 50.0 166.8 23,530 21 60 14. 65 28.5 14.50 60.0 1.5 14. 65 14. 65 28.5 21. 60.0 1.5 14. 65 129.6 75.0 166.8 24,980 22F 60E.-- 14. 65 28.5 21.75 60.0 1.5 14. 65 14. 65 28.5 29.0 60.0 1.5 14. 65 129.6 100.0 166.8 26,430 2352. 601]... 14. 65 28.5 29.0 60.0 1.5 14. 65 14. 65 28.5 36.25 60.0 1.5 14. 65 129.6 125.0 166.8 27,880 24111- 60 14.65 28.5 36.25 60.0 1.5 14.65 14. 65 28.5 43. 50 60.0 1.5 14. 65 129.6 150.0 166.8 20, 25F. 64E..- 15.25 20.4 63.0 1.5 15.25 15. 25 20.4 15.0 63.0 1.5 15.25 92.8 51.7 175.2 22810 26R. 64 15.25 20.4 15.0 63.0 1.5 15.25 15.25 20.4 20.0 63.0 1.5 15.25 92.8 68.95 1752 23,810 27E. 64E... 15.25 20.4 20.0 63.0 1.5 15.25 15.25 20.4 25.0 63.0 1.5 15.25 92.8 86.15 1752 24.810 28F 64 15.25 20.4 25.0 63.0 1.5 15.25 15.25 20.4 30.0 63.0 1.5 15.25 92.8 103.4 1752 25,810 29F. 64E 15. 25 20.4 30.0 63.0 1.5 15. 25 15. 25 20.4 35.0 63.0 1.5 15. 25 92.8 120. 65 175 2 26,810 30F 64E.-- 15. 25 20.4 35.0 63.0 1.5 15.25 15. 25 20.4 40.0 63.0 1.5 15. 25 92.8 137.9 175 2 27,810 31F- 69 14.15 14.1 63.0 1.5 14.15 14.15 14.1 7.0 63.0 1.5 14.15 64.2 24.1 1750 19,656 32F 69E 14.15 14.1 7.0 63.0 1.5 14.15 14.15 14.1 14.0 63.0 1.5 14.15 64.2 48.2 175 0 21,056 33F" 69 14.15 14.1 14.0 63.0 1.5 14.15 14.15 14.1 28.0 63.0 1.5 14.15 64.2 96.4 1750 22,456 34F.. 69E-.- 14.15 14.1 28.0 63.0 1.5 14.15 v14. 15 14.1 35.0 63.0 1.5 14.15 64.2 120.5 175 0 23,856 35F 69 14.15 14.1 35.0 63.0 1.5 14.15 14.15 14.1 42.0 63.0 1.6 14.15 64.2 144.6 1750 25,256 3611. 69E--- 14.15 14.1 42.0 63.0 1.5 14.15 14.15 14.0 56.0 63.0 1.5 14.15 64.2 192.8 1750 26,656

Table X Ex. Max. Max. Time, Solubility No. temp., pres., hrs.

C. p. s. 1. Water Xylene Kerosene -130 10-15 y Insoluble Soluble- Insoluble. 125-130 10-15 d0. d D0. 125-130 10-15 Emulslfiable.. Do. 125-130 10-15 do Do. 125-130 10-15 2 D0. 125-130 10-15 5 D0. 125-130 10-15 56 Do. 125-130 10-15 16 Do. 125-130 10-15 56 D0. 125-130 10-15 1% D0. 125-130 10-15 2 D0. 125-130 10-15 3 D0. 125-130 10-15 $6 D0. 125-130 10-15 96 Do. 125-130 10-15 36 D0. 125-130 10-15 1% Do. 125-130 10-15 .2 Do. 125-130 10-15 3 do Do. 125-130 10-15 2 Soluble. D0. 125-130 10-15 2 d do- Do. 125-130 10-15 3 do Do. 125-130 10-15 3 d0 D0. 125-130 10-15 3% d0 Soluble. 125-130 10-15 8% d0 125-130 10-15 2 do Insoluble. 125-130 10-15 2 do- 0. 125-130 10-15 2% ......do.. Do. 125-130 10-15 3 d0 125-130 10-15 3% d0 125-130 10-15 4 125-130 10-15 2 125-130 10-15 2 125-130 10-15 2 125-130 10-15 3 125-130 10-15 6 125-130 10-15 4 -150 10-15 A 145-150 10-15 1% 145-150 10-15 2 145-150 10-15 3% 145-150 10-15 3 145-150 10-15 6 145-150 10-15 M 145-150 10-15 1 145-150 10-15 2 145-150 10-15 2% 145-150 10-15 3 145-150 10-15 6 145-150 10-15 1 145-150 10-15 1 145-150 10-15 2 145-150 10-15 2 145-150 10-15 2% 145-150 10-15 7% ..-.-.(10-..

33 Emily that no effort is made to obtain colorless resins initially and the resins themselves may be yellow, amher, or even dark amber. Condensation of a nitrogenous product invariably yields a darker product than the original resin and usually has a reddish color. The solvent employed, if xylene, adds nothing to the color but one may use a darker colored aromatic petroleum solvent. Oxyalkylation generally tends to yield lighter col- 34 ored products and the more oxide employed the lighter the color of the product. Products can be prepared in which the final color is a lighter amber with a reddish tint. Such products can be decolorized by the use of clays, bleaching chars, etc. As far as use in demul'sification is concerned, or some other industrialuses, there is no justification for the cost of bleaching the product. Generally speaking, the amount of alkaline catalyst Table XI Max. Max. Solubility Ex. P Tlme, No. p. s. i. hrs.

Water Xylene Kerosene 10-15 4% Eulsifiable.. Insoluble. 10-15 2 d0 D0. 10-15 2 d0 D0. 10-15 Insoluble. Do'. 10-15 do. Do. 10-15 D0. 10-15 D0. 10-15 D0. 10-15 Do. 10-15 D0. 10-15 Do. 10-15 D0. 10-15 D0. 10-15 Do. 10-15 D0. 10-15 Do. 10-15 D0. 10-15 Soluble. 10-15 Do. 10-15 D0. 10-15 D0. 101 5 Insoluble 1045 Do. 10-15 D0. 10-15 Soluble; 10-15 D0. 1 0-l5 Insoluble 10-15 D0 15-10 Do; 10-15 DO. 10-15 Soluble. 10-15 D0. 10-15 D0. 10-15 do-. Insoluble. 10-15 Emulsifiable. D0. 10-15 d Do. 10-15 D0. 10-15 "D0. 10-15 D0. 10-15 Do. 10-15 D0. 10-15 Do. 10-15 Do. 10-15 D0. 10-15 D0. 10-15 D0. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 D0. 10-15 D0. 10-15 Do. 10-15 Do. 10-15 D0. 10-15 Soluble. 10-15 Insoluble. 10-15 D0. 10-15 Do. 10-15 D0. 10-15 D0. 10-15 Soluble 10-15 Insoluble 10-15 D0. 10-15 Do. 10-15 Do. 10-15 Do. 10-15 Soluble. 10-15 Insoluble. 10-15 D0. 1 0-15 Do. 10-15 D0. 10-15 Do. 10-15 Soluble. 10-15 D0. 10-15 Do. 10-15 D0. 10-15 D0. 10-15 D0. 10-15 Do. 10-15 Do. 10-15 D0. 10-15 D0. 10-15 Do. 10-15 Do. 10-15 D0. 10-15 D0. 10-15 D0. 10-15 Do. 10-15 D0. 10-15 Do.

Table XII Max. Max Solubility Ex. temp., pres Time, No. 0. p. s. 1. hrs.

Water Xylene Kerosene 10-15 18% 10-15 1 10-15 1 1015 1% 10-15 2 10-15 2 10-15 20 10-15 1% 10-15 1% 10-15 2 10-15 2% 10-15 3 1015 23% 10-15 1 10-15 2 10-15 2 10-15 2% 10-15 3 10-l5 28 10l5 2 10-15 2% 10-15 3 10-15 3 10-15 3% 10-15 22% 10-15 2% 10-15 3 10-l5 3% 10-15 4 10-15 5 -15 1015 2% 10-15 3 10-15 3% 10-15 4 10-15 5 PART 7 As to the use of conventional demulsifying agents reference is made to U. S. Patent No. 2,626,929, dated I anuary 7, 1953, to De Groote, and particularly to Part 3. Everything that appears therein applies with equal force and effect to the instant process, noting only that where reference is made to Example 13!) in said text beginning in column 15 and ending in column 18, reference should be made to Example 5D, herein described.

PART 8 The products, compounds or the like, herein described can be employed for various purposes and particularly for the resolution of petroleum emulsions of the water-in-oil type as described in detail in Part 7, preceding.

Such products can be reacted with alkylene imines, such as ethylene imine or propylene imine, to produce cationactive materials. Instead of an imine one may employ what is somewhat equivalent material, to wit, a dialkylaminoepoxypropane of the structure l /R' Hz N wherein R and R are alkyl groups.

It is not necessary to point out that, after reaction with a reactant of the kind described which introduces a basic nitrogen atom, the resultant product can b em ployed for the resolution of emulsions of the water-in-oil type as described in Part 7, preceding, and also for other purposes described hereinafter.

Referring now to the use of the products obtained by reaction with a polyepoxide and certain specified oxyalkylated products obtained in the manner described in Part 6, preceding, it is to be noted that in addition to their use in the resolution of petroleum emulsions they may be used as emulsifying agents for oils, fats, and waxes, as ingredients in the laundering, scouring, drying, tanning and mordanting industries. They may also be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, for pharmaceutical purposes.

Not only do these oxyalkylated derivatives have utility as such but they can serve as initial materials for more complicated reactions of the kind ordinarily requiring a hydroxyl radical. This includes esterification, etherization, etc.

The oxyalkylated derivatives may be used as valuable additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils. Also, they can be used as additives to hydraulic brake fluids of the aqueous o and non-aqueous types. They may be used in connection with other processes where they are injected into an oil or gas well for purpose of removing a mud sheath, increasing the ultimate flow of fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood waters. These derivatives also are suitable for use in dry cleaners soaps.

More specifically, such products, depending on the nature of the initial resin, the particular monoepoxide selected, and the ratio of monoepoxide to resin, together with the particular polyepoxide employed, result in a variety of materials which are useful as wetting agents or surface tension reducing agents; as detergents, emulsifiers or dispersing agents; as additives for lubricants, both of the natural petroleum type and the synthetic type, as additives in the flotation of ores, and at times as aids in chemical reactions insofar that demulsification is produced between the insoluble reactants. Furthermore, such products can be used for a variety of other purposes, including use as corrosion inhibitors, defoamers, asphalt addi tives, and at times even in the resolution of oil-in-water emulsions. They serve at times as mutual solvents promoting a homogeneous system from two otherwise insolublephases.

The productsherein described can be reacted with polycarboxy acids such as phthalic acid, or: anhydride, maleic acid or anhydride, diglycolic acid, and various tricarboxy and tetracarboxy acids so as to yield acylated derivatives particularly if one employs one mole of the polycarboxy acid for each reactive hydroxyl radical presentin the'final polyepoxidetreated product. Thus, one obtains acomparatively large molecule in which there is a plurality of carboxyl radicals. Such acidic fractional esterslaresuitable for the resolution of petroleum emulsions bf the water-in-oil type as herein described.

Havingthus described our invention, what we claim as new: and desirev tosecure by'Letters Patent is:

1. A 3-step manufacturing method involving (1) con densation; (2) oxyalkylation with a polyepoxide; and (3) oxyalkylation with a monoepoxide; said first step being that of (A) condensing (a) a fusible, nonoxygenated organic solvent-soluble, water-insoluble, phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absenceof trifunctional phenols; said phenol being of theformula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated polyamine having at leastone secondary amino group and having up to 32 carbon atoms in any radical attachedto any aminonitrogen atom, and with the further proviso that the polyamine be free from any primary aminoradical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat stable; followed as a second step by (B) reacting said resin condensate with nonaryl hydrophile polyepoxides containing twoterminal l',2-epoxy rings obtained by replacement of an oxygen-linked hydrogen atom in a water-soluble polyhydric alcohol by the radical H H H -O-OGH said polyepoxides being free from reactive functional groups other than 1,2-epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting solvent-soluble liquids and solids melting below the point of pyrolysis; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the resin condensate to 1 mole of the polyepoxide, and then completing the reaction by a third step of (C) reacting said polyepoxide- 38 derivedproduct with a monoepoxide; said monoepox-ide being an alpha-beta alkylene oxide having. not more than 4"carbo n atoms and selectedfromthe class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

2; The product obtained by the method described in claim 1'; v

3. A, 3'-step manufacturing method involving (1') condensation; (2) oxyalkylation with a polyepoxide; and (3) oxyalkylation with a rnonoepoxide; said first step being that of (A) condensing (a) a. fusible, nonoxygenated or ganic solvent-soluble, water-insoluble, phenol-aldehyde resin havingan average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resinmolecule; said resin being difunctional only in regard to methylol-forming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol beingof the formulav l polyamine having at least one secondary amino group and having up to 32 carbon atomsin any radical attached to any amino nitrogen atom,. and with the further proviso that the polyamine be free from any primary amino 35 radical, any substituted imidazoline radical and any substituted tetrahyd'ropyrimidine radical; and (c) formaldehyde; said, condensation reaction being conducted at a temperaturesufficiently high-to eliminate water. and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat stable followed as a second step by (B) reacting said resin condensate with nonaryl hydrophile polyepoxides containing at least two 1,2-epoxy rings and having two terminal l,2-epoxy rings obtained by replacement of an oxygenlinked hydrogen atom in a water-soluble polyhydric alcohol by the radical said polyepoxides being free from reactive functional groups other than, l,2.-epoxy and hydroxyl groups and.

characterized by the fact. that the divalent linkage uniting the terminal. oxirane rings is free from any radical having more than 4: uninterrupted carbon atoms in a single chain; said polyepoxides being characterized by having present not more than 20 carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting solvent-soluble liquids and solids melting below the point of pyrolysis; With the added proviso that the reaction product be a member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the resin condensate to 1 mole of the polyepoxide, and then completing the reaction by a third step of (C) reacting said polyepoxide-derived product with a monoepoxide; said monoepoxide being an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

4. A 3-step manufacturing method involving (1) condensing; (2) oxyalkylation with a diepoxide; and (3) oxyalkylation with a monoepoxide; said first step being that of (A) condensing (a) a fusible, nonoxygenated organic solvent-soluble, water-insoluble, phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and analdehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having up to 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical, and any substituted tetrahydropyrimidine radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable followed as a second step by (B) reacting said resin condensate with nonaryl hydrophile diepoxides containing two terminal 1,2-epoxy rings obtained by replacement of an oxygen-linked hydrogen atom in a water-soluble polyhydric alcohol by the radical H H H -CC--CH said diepoxides being free from reactive functional groups other than 1,2-epoxy and hydroxyl groups and characterized by the fact that the divalent linkage uniting the terminal oxirane rings is free from any radical having more than 4 uninterrupted carbon atoms in a single chain; said diepoxides being characterized by having present not more than 20 carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of nonthermosetting solvent-soluble liquids and solids melting below the point of pyrolysis; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the resin condensate to 1 mole of the diepoxide', and then completing the reaction by a third step of (C) reacting said diepoxide-derived product with a monoepoxide; said monoepoxide being an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

5. The method of claim 4 wherein the diepoxide contains at least one reactive hydroxyl radical.

6. A 3-step manufacturing method involving (1) condensation; (2) oxyalkylation with a diepoxide, and (3) oxyalkylation with a monoepoxide; said first step being that of (A) condensing (a) a fusible, nonoxygenated or-' in which R is a saturated aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) a basic hydroxylated polyamine having at least one secondary amino group and having up to 32 carbon atoms in any radical attached to any amino nitrogen atom, and with the further proviso that the polyamine be free from any primary amino radical, any substituted imidazoline radical; and (c) formaldehyde; said condensation reaction being conducted at a temperature sufficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous condensation product resulting from the process be heat-stable; followed as a second step by (B) reacting said resin condensate with a hydroxylated diepoxypolyglycerol containing two terminal 1,2-epoxy rings and having not more than 20 carbon atoms; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non-thermosetting solvent-soluble liquids and solids melting below the point of pyrolysis; with the added proviso that the reaction product be a member of the class of solvent-soluble liquids and solids melting below the point of pyrolysis; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction; and with the final proviso that the ratio of reactants be 2 moles of the resin condensate to 1 mole of the diepoxide; and then completing the reaction by a third step of (C) reacting said diepoxide-derived product with a monoepoxide; said monoepoxide being an alpha-beta alkylene oxide having not more than 4 carbon atoms and selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide and methylglycide.

7. The method of claim 6 wherein the polyglycerol derivative has not over 5 glycerol nuclei, and the precursory phenol is para-substituted and contains at least 4 and not over 14 carbon atoms in the substituent group, and the precursory aldehyde is formaldehyde, and the total number of phenolic nuclei in the initial resin are not over 5.

No references cited. 

1. A 3-STEP MANUFACTURING METHOD INVOLVING (1) CONDENSATION; (2) OXYALKYLATION WITH A POLYEPOXIDE; AND (3) OXYALKYLATION WITH A MONOEPOXIDE; SAID FIRST STEP BEING THAT OF (A) CONDENSING (A) A FUSIBLE, NONOXYGENATED ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE, PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 